The present invention relates to a method for the deposition of a thin film onto a substrate by the technique of Atomic Layer Deposition.
In the technique of Atomic Layer Deposition a substrate is exposed sequentially and alternately to at least two mutually reactive reactants. The substrate is heated to a temperature that is high enough to prevent condensation of the reactants but low enough to prevent thermal decomposition of each of the reactants. The substrate is exposed to the first reactant and the first reactant is chemisorbed onto the surface of the substrate until the surface is occupied with a monolayer of the first reactant. Then the chemisorption saturates and excess reactant is exhausted. Then the supply of the first reactant is cut-off and the reaction chamber is evacuated and/or purged to remove the traces of non-chemisorbed first reactant from the gas phase. Then the substrate is exposed to the second reactant which reacts with the chemisorbed first reactant under the formation of a solid film and the release of gaseous reaction products until the monolayer of the first reactant has fully reacted with the second reactant and the surface of the substrate is covered with a chemisorbed monolayer of the second reactant. Then the process saturates and excess of the second reactant is exhausted. This cycle can be repeated a number of times until a sufficiently thick film has been deposited onto the substrate. More than two reactants can be used, in particular for the deposition of ternary or more complicated compounds or multilayers. This technique has been know since 1980, see the review article of Suntola, xe2x80x9cAtomic Layer Epitaxyxe2x80x9d in: xe2x80x9cHandbook of Christal Growth 3, Thin Films and Epitaxy, part B. Growth Mechanisms and Dynamicsxe2x80x9d, by D. T. J. Hurle, Ed. Elsevier, 1994, Chapter 14, p 601-663. Because only a monolayer of the material is deposited per cycle, a sufficient number of cycles needs to be executed to achieve the required film thickness. In order to minimize the cycle time without compromising the effectiveness of the purging of the reactor, the volume of the reactor has been minimized and the flow dynamics of the reactor has been optimized.
A first example of a reactor is given in U.S. Pat. No. 5,711,811 which is incorporated herein by reference. This patent describes a reactor in which a plurality of substrates can be processed simultaneously. In this reactor, a stack of narrowly spaced substrates is formed and the direction of the gas flow is parallel to the main surfaces of the substrates, an inlet located at one side of a substrate surface and the exhaust located at the other side of the substrate surface. Although it is an advantage that a plurality of substrates can be processed simultaneously, making the relatively slow technique more economical, it is a disadvantage that the formation of the stack of substrates needs to be carried out manually. In Finnish patent application 991078 of Microchemistry Oy a single wafer reactor for Atomic Layer Deposition is described which allows robotic loading and unloading of the substrate. The disadvantage of this reactor is that only one wafer is processed at a time, using the relatively slow Atomic Layer Deposition technique.
It is the object of the present invention to overcome these disadvantages and provide a method for operating the Atomic Layer Deposition technique that allows batch processing and robotic handling of the wafers.
In accordance with one aspect of the invention, the Atomic Layer Deposition process is operated in a vertical hot wall LPCVD batch reactor. In such a reactor the lower end of the vertically elongated reaction chamber is provided with an opening for insertion and removal of a boat wlich comprises a number of mutually spaced supports to support the substrates in the horizontal orientation and wherein the stack of mutually spaced substrates extends in the vertical direction. The reaction chamber is provided with at least one reactant inlet and a reactant exhaust so that a flow in the vertical direction is created. In the vertical direction the transport of reactants is determined by forced convective gas flow from the inlet end of the reactor towards the exhaust end of the reactor. In the narrow gap between the substrates, the transport of reactants is determined by diffusion. This occurs at a slower rate than the transport in the vertical direction. However, because of the large number of substrates, typically 50 to 200, cycle times which are an order of magnitude larger than the cycle times in a single wafer reactor can easily be accepted.
In normal Atomic Layer Deposition enough reactant needs to be supplied to saturate all the available surface sites with reactant. In the method of the present invention, in addition to this requirement, the supplied reactant should be given the opportunity to distribute itself over the whole batch of wafers. To this end the present invention proposes to supply the reactant, eventually mixed with an inert gas like nitrogen, at one end of the reaction chamber while pumping at the other end of the reaction chamber such that during the period of supply of the reactant the volume of the reaction chamber is replaced a sufficient amount of times to reach even distribution but not so often that the required time per pulse becomes uneconomically long. Therefore it is proposed to replace the volume of the reactor during the period of supply of the reactant at least one time to a maximum of 50 times, taken into account the average pressure in the reaction chamber during the period of supply of the reactant.
In a preferred embodiment it is proposed that during the time in between successive reactant pulses the reactor is evacuated and at least during part of this time an inert gas is fed into the reactor to drive the previous reactant pulse out of the annular space of the reactor while additionally during part of this time a pressure in the reactor is lower than the average pressure during the reactant exposure to allow diffusion of the reactant out of the narrow gap between the substrates.
In an alternative embodiment, following the Atomic Layer Deposition treatment, the substrate is possibly heated to a second temperature and reactants for a chemical vapor deposition process are introduced into the reactor. After completion of the deposition by chemical vapor deposition the supply of reactants is cut off and after evacuating and/or purging the reaction chamber and when required backfilling it to atmospheric pressure, the substrate is removed from the reaction chamber.